基于反应模板与分子动力学的胺基相变吸收剂分相预测方法

doi:10.11949/0438-1157.20241178

化工学报 ›› 2025, Vol. 76 ›› Issue (5): 2387-2396.DOI: 10.11949/0438-1157.20241178

基于反应模板与分子动力学的胺基相变吸收剂分相预测方法

陈建兵¹(), 常昊², 高明¹, 邢兵¹, 张磊²^,³, 刘奇磊²^,³()

^1.中石化（大连）石油化工研究院有限公司，辽宁大连 116045
^2.大连理工大学化工学院，化工系统工程研究所，制药工程系，智能材料化工前沿科学中心，精细化工全国重点实验室，辽宁大连 116024
^3.大连理工大学宁波研究院，浙江宁波 315016

收稿日期:2024-10-23 修回日期:2025-02-14 出版日期:2025-05-25 发布日期:2025-06-13
通讯作者: 刘奇磊
作者简介:陈建兵（1982—），男，硕士，副研究员，chenjianbing.fshy@sinopec.com
基金资助:
国家自然科学基金青年科学基金项目(22208042);大连市青年科技之星项目(2023RQ059);中央高校基本科研业务费项目(DUT24RC(3)042)

Phase separation prediction methodology for amine-based phase change absorbents based on reaction templates and molecular dynamics

Jianbing CHEN¹(), Hao CHANG², Ming GAO¹, Bing XING¹, Lei ZHANG²^,³, Qilei LIU²^,³()

^1.SINOPEC (Dalian) Research Institute of Petroleum and Petrochemicals Co. , Ltd. , Dalian 116045, Liaoning, China
^2.State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Department of Pharmaceutical Sciences, Institute of Chemical Process Systems Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^3.Ningbo Institute of Dalian University of Technology, Ningbo 315016, Zhejiang, China

Received:2024-10-23 Revised:2025-02-14 Online:2025-05-25 Published:2025-06-13
Contact: Qilei LIU

摘要/Abstract

摘要：

碳捕集技术发展对于缓解全球变暖至关重要。胺基相变吸收剂凭借其解吸能耗小等优势，常用于化学吸收二氧化碳。然而，相变吸收剂配方成分复杂、分相机制不清、实验成本高昂，限制了新型高性能相变吸收剂的敏捷开发。对此，提出一种基于反应模板与分子动力学的胺基相变吸收剂分相预测方法，通过构建反应模板，自动生成化学吸收产物，进而利用分子动力学方法与径向分布函数等指标，研究胺基相变吸收剂的分相机制并预测其分相行为。所提方法编译为一套可全自动化预测相变吸收剂分相行为的软件及可视化界面，并应用于七种不同相变吸收剂体系，分相行为预测结果均与实验结果吻合，且发现有机溶剂与水分子之间的氢键作用是影响相变吸收剂分相行为的关键因素。本文研究成果可从计算角度辅助预测胺基相变吸收剂的分相行为，有助于降低实验测试成本，加速新型高性能相变吸收剂的开发。

关键词: 二氧化碳捕集, 有机胺, 相变吸收剂, 分子模拟, 相平衡

Abstract:

The development of carbon capture technology is crucial for mitigating global warming. Amine-based phase change absorbents are often used for chemical absorption of carbon dioxide due to their advantages such as low desorption energy consumption. However, the complexity of phase change absorbent formulations, unclear phase separation mechanisms, and high experimental costs limit the rapid development of novel high-performance phase change absorbents. To this end, this paper proposes a phase separation prediction methodology for amino-based phase change absorbents based on reaction templates and molecular dynamics. By constructing reaction templates, chemical absorption products are automatically generated. Molecular dynamic methods and indicators such as radial distribution functions are further employed to study the phase separation mechanisms of amino-based phase change absorbents and predict their phase separation behaviors. The proposed method is compiled into a fully automated software for predicting phase separation behaviors of phase change absorbents, complete with a visualization interface. This method has been applied to seven different phase change absorbent systems, with the predicted phase separation behaviors aligning with experimental results. It is also discovered that the hydrogen bonding interactions between organic solvents and water molecules are key factors influencing the phase separation behavior of phase change absorbents. The above studies assist in predicting the phase separation behavior of amino-based phase change absorbents from a computational perspective, which helps to reduce the cost of experimental testing and accelerate the development of novel high-performance phase change absorbents.

Key words: CO₂ capture, amine, phase change absorbent, molecular simulation, phase equilibrium

中图分类号:

TQ 028.8

陈建兵, 常昊, 高明, 邢兵, 张磊, 刘奇磊. 基于反应模板与分子动力学的胺基相变吸收剂分相预测方法[J]. 化工学报, 2025, 76(5): 2387-2396.

Jianbing CHEN, Hao CHANG, Ming GAO, Bing XING, Lei ZHANG, Qilei LIU. Phase separation prediction methodology for amine-based phase change absorbents based on reaction templates and molecular dynamics[J]. CIESC Journal, 2025, 76(5): 2387-2396.

图/表 9

图1 胺基相变吸收剂分相预测方法流程图

Fig.1 The flowsheet of the phase separation prediction methodology for amino-based phase change absorbents

图2 SimuLab软件界面

Fig.2 The software interface of SimuLab

表1 CO2相变吸收剂溶液组成与模拟结果

Table 1 Compositions of CO2 phase change absorbent solutions and simulation results

组别	组分A （质量分数）	组分B （质量分数）	组分C （质量分数）	组分D （质量分数）	温度/K	实验结果	模拟结果
1	30% MEA	40% 正辛醇	20% NMP	10% 水	313.15	分相	X=20%、50%、80%均分相
2	30% MEA	5% 正辛醇	55% NMP	10% 水	313.15	不分相	X=20%、50%、80%均不分相
3	30% MDEA	30% 正庚醇	15% NMP	20% 水	313.15	分相	X=20%、50%、80%均分相
4	5% DEA	25% MDEA	40% 环丁砜	30% 水	313.15	分相	X=20%、50%、80%均分相
5	5% AMP	25% MDEA	40% 环丁砜	30% 水	313.15	分相	X=20%、50%、80%均分相
6	5% PZ	25% MDEA	40% 环丁砜	30% 水	313.15	分相	X=50%、80%分相，X=20%不分相
7	30% MEA	10% 正辛醇	50% NMP	10% 水	313.15	分相	X=80%分相，X=20%、50%不分相

图3 组别3分子动力学模拟反应前后结构[（a）初始结构；（b）模拟后结构；X=50%]

Fig.3 The structures of molecular dynamic simulation before and after reaction for group 3 [(a) the initial structure; (b) the structure after simulation; X=50%]

图4 水分子数量变化图

Fig.4 The quantity variations for water molecules

图5 组别1径向分布函数图（X=50%）

Fig.5 The radial distribution function for group 1 (X=50%)

图B1 组别1、2、4、5、6、7分子动力学模拟反应前后结构[（a）为初始结构；（b）为模拟后结构；组别1、2、4、5、6：X=50%；组别7：X=80%]

Fig. B1 The structures of molecular dynamic simulation before and after reaction for group 1, 2, 4, 5, 6, 7 [(a) is the initial structure; (b) is the structure after simulation; groups 1, 2, 4, 5, 6: X=50%; group 7: X=80%]

图C1 组别3、4、5水分子数量图

Fig.C1 The quantity variations for water molecules in group 3, 4, 5

图D1 组别2~7径向分布函数图（组别2~6：X=50%；组别7：X=80%）

Fig. D1 The radial distribution function for group 2—7 (groups 2—6: X=50%; group 7: X=80%)

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基于反应模板与分子动力学的胺基相变吸收剂分相预测方法

Phase separation prediction methodology for amine-based phase change absorbents based on reaction templates and molecular dynamics

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